Aminated γ-dialdehyde; methods for preparing the same and cosmetic compositions containing the same

ABSTRACT

Aminated γ-dialdehyde and the quaternary ammonium salts thereof are prepared by acid hydrolysis of their respective corresponding 2,5-dialkoxy 3-amino 4-hydroxy tetrahydrofurans or by acid hydrolysis of their respective corresponding tetraalkyl acetals. The aminated γ-dialdehydes and the quaternary ammonium salts thereof are usefully employed in cosmetic compositions to tan the skin or to strengthen or restructure the hair.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a divisional application of Ser. No. 750,518, filed Dec. 14,1976 now U.S. Pat. No. 4,118,423, which in turn is a divisionalapplication of Ser. No. 463,808, filed Apr. 24, 1974, now U.S. Pat. No.4,014,990, which in turn is a division of Ser. No. 210,217, filed Dec.20, 1971, now U.S. Pat. No. 3,812,246.

The present invention relates to a γ-dialdehyde having the formula##STR1## wherein R₁ and R₂ each independently are selected from thegroup consisting of hydrogen, alkyl, hydroxyalkyl, cycloalkyl, aryl,alkaryl, (2,5-dialkoxy-4-hydroxy)-3-tetrahydrofuryl wherein each of thealkoxy moieties has 1-4 carbon atoms,β-N-[(2,5-dialkoxy-4-hydroxy)-3-tetrahydrofuryl]-aminoethyl wherein eachof the alkoxy moieties has 1-4 carbon atoms, and together with thenitrogen atom to which they are attached form a heterocycle selectedfrom the group consisting of piperdinyl and morpholinyl. Representativealkyl substituents are those having 1-6 carbon atoms while usefulhydroxalkyl substituents are those wherein the alkyl moiety has 1-6carbon atoms such as hydroxyethyl. Representative cycloalkylsubstituents include those having 3-6 carbon atoms and especiallycyclohexyl, whereas useful aryl substituents include phenyl, naphthyland the like. The alkyl moiety of the alkaryl substituent can have,preferably, from 1-6 carbon atoms while the aryl moiety can be, forinstance, phenyl, naphthyl or the like. A preferred alkaryl substituentis benzyl.

The present invention also relates to the quaternary ammonium salts ofthe γ-dialdehydes of formula (I), said quaternary ammonium salts havingthe formula ##STR2## wherein R₁ and R₂ each independently are selectedfrom the group consisting of alkyl, hydroxyalkyl, cycloalkyl, aryl,alkaryl, (2,5-dialkoxy 4-hydroxy)-3-tetrahydrofuryl wherein each of thealkoxy moieties has 1-4 carbon atoms, β-N-[(2,5-dialkoxy4-hydroxy)-3-tetrahydrofuryl]-aminoethyl wherein each of the alkoxymoieties has 1-4 carbon atoms, and together with the nitrogen atom towhich they are attached form a heterocycle selected from the groupconsisting of piperidinyl and morpholinyl. Representative alkylsubstituents are those having 1-6 carbon atoms and, advantageously,methyl or ethyl. Useful hydroxyalkyl substituents are those wherein thealkyl moiety has 1-6 carbon atoms, such as hydroxyethyl. Representativecycloalkyl substituents include those having 3-6 carbon atoms and,especially, cyclohexyl. The alkyl moiety of the alkaryl substituent canhave, preferably, from 1-6 carbon atoms while the aryl moiety again canbe phenyl, naphthyl or the like. A preferred alkaryl substituent isbenzyl. R₃ represents a member selected from the group consisting oflower alkyl having 1-4 carbon atoms and benzyl, substituted or not andX⁻ represents a member selected from the group consisting of chloride,bromide, iodide, methosulfate, ethosulfate, paratoluene sulfonate andmethane sulfonate. A preferred value for R₃ is methyl while preferredvalues for X⁻ are chloride, methosulfate, paratoluene sulfonate andmethane sulfonate.

The above γ-dialdehydes of formulae (I) and (II) correspond to2-amino-3-hydroxy aldehyde and to the N-substituted derivatives thereof.

The present invention also relates to the preparation of theγ-dialdehydes having formula (I) and of the quaternary ammonium saltsthereof having formula (II).

Further, the present invention also relates to a cosmetic compositioncontaining at least one animated γ-dialdehyde having formula (I) and/orat least one quaternary ammonium salt thereof having formula (II).

The aminated γ-dialdehydes of formula (I) can be prepared by acidhydrolysis of a 2,5-dialkoxy-3-amino 4-hydroxytetrahydrofuran and theN-substituted derivatives thereof having formula ##STR3## wherein R₁ andR₂ have the same meanings as in formula (I) and R represents alkylhaving 1 to 4 carbon atoms, preferably, methyl.

The quaternary ammonium salts of aminated γ-dialdehyde having formula(II) can be prepared by acid hydrolysis of the quaternary ammonium saltsof N-disubstituted 2,5-dialkoxy 3-amino 4-hydroxy tetrahydrofuranshaving the following formula ##STR4## wherein R₁, R₂, R₃ and X⁻ have themeaning indicated above for the compounds of formula (II) and Rrepresents an alkyl having 1-4 carbon atoms, preferably methyl.

In the acid hydrolysis reaction medium the concentration of the compoundhaving formula (III) or (IV) to be hydrolyzed can vary within widelimits and, preferably, a concentration of 0.01 to 1 mole/liter isemployed.

There is heated, for example, in a boiling water bath, an acid solutionof the compound having formula (III) or (IV) for a time that can rangefrom about 5 minutes to several hours. The acid medium is obtained byaddition of a strong mineral or organic acid, such as HCl, H₂ SO₄,paratoluene sulfonic acid or methane sulfonic acid up to a concentrationof about 0.1 to 5 N. The reaction mass is generally heated to atemperature of about 20° to 100° C.

The aminated γ-dialdehydes of formulae (I) and (II) can also be preparedby acid hydrolysis of their corresponding tetraalkyl acetals havingformulae (V) and (VI), respectively ##STR5##

In formula (V), R₁ and R₂ have the meanings indicated for the compoundof formula (I) and R represents an alkyl having 1-4 carbon atoms,preferably methyl. In formula (VI) R₁, R₂, R₃ and X⁻ have the meaningsindicated for the compounds of formula (II) and R represents an alkylhaving 1-4 carbon atoms, preferably methyl.

Once the hydrolysis reaction has been terminated, these solutionsrespectively, contain aminated γ-dialdehydes of formula (I) orquaternary ammonium salts of formula (II) depending on whether thestarting compound was of formula (III) or (V), or a compound of theformula (IV) or (VI).

The solutions which result from the hydrolysis reaction yieldcharacteristic reactions of aldehydes, such as reduction of hypoiodite,formation of oximes and dinitrophenylhydrazones.

The aldehydes in the hydrolyzed solutions are characterized either bytheir reaction with dinitrophenylhydrazine to produce adinitrophenylhydrazone or by hypoiodite determination.

In the first case there is employed an excess of solution of 0.2%2,4-dinitrophenylhydrazine in 2N HCl, and after a period of standing thedinitrophenylhydrazones that are formed are separated by filtration.They are then washed with 2 N HCl, dried and analysed.

In the second case the procedure followed is that embodied in the methodadopted by Robinson and McLeod, which is described in Loiseleur's book,"Laboratory Technique", page 1344 (Masson Edition).

The aminated γ-dialdehydes of formula (I) are only stable in stronglyacid solution, with the primary amino compounds being less stable thanthe secondary and tertiary compounds.

It is to be noted that the 2,5-dilkoxy tetrahydrofuran and theirderivatives represented by formulae III and IV present cis-transisomerism at the level of the alkoxy groups in positions 2 and 5. Thesubstituents in positions 3 and 4 can likewise increase the number ofpossible isomers. The isomers often are detectable by gas chromatographyand sometime they can be isolated by fractional distillation.

Certain of the 2,5-dialkoxy tetrahydrofurans of formula (III) are newcompounds. They are those wherein R represents alkyl having 1 to 4carbon atoms, preferably the methyl radical; and wherein R₁ representshydroxyalkyl, cycloalkyl, aryl, alkaryl radical having up to 12 carbonatoms, (2,5-dialkoxy 4-hydroxy)-3-tetrahydrofuryl and β-N-[(2,5-dialkoxy4-hydroxy)-3-tetrahydrofuryl]-aminoethyl and wherein R₂ representshydrogen or the immediately above meaning indicated for R₁. In these newtetrahydrofurans, the alkyl moiety is hydroxyalkyl and the cycloalkylradical preferably is cyclohexyl, while the preferred aryl substituentis phenyl, the preferred hydroxyalkyl substituent is hydroxyethyl andthe preferred alkaryl substituent is benzyl.

2,5-dialkoxy 3-amino 4-hydroxy tetrahydrofurans especial 2,5-dimethoxy3-amino 4-hydroxy tetrahydrofurans, and the N-substituted derivativesthereof having formula (III), quaternary ammonium salts having formula(IV), tetraalkyl acetal having formula (V) and quaternary ammonium saltsof tetraalkyl acetals having formula (VI) are valuable intermediateproducts which by way of acid hydrolysis allow to obtain usefulsolutions for the preparation of cosmetic compositions, particularly forthe coloring of the skin and the strengthening or the restructuring ofthe hair.

The salts of the 2,5-dialkoxy 3-ammonio 4-hydroxy tetrahydrofurans offormula (IV) are also new compounds.

Moreover, the aminated γ-dialdehydes of formula (I) and their quaternaryammonium salts having formula (II) are also new compounds.

The 2,5-dialkoxy tetrahydrofurans and their N-substituted derivatives offormula (III) can be prepared according to the following methods A andB.

METHOD A

Reaction of an amine having the formula ##STR6## wherein R₁ and R₂ havethe meanings indicated for the compound of formula (III) on a2,5-dialkoxy-3, 4-epoxytetrahydrofuran having formula (VIII) wherein Rrepresents alkyl having 1 to 4 carbon atoms. ##STR7##

The 2, 5-dialkoxy-3,4-epoxy tetrahydrofuran of formula (VIII) can, inturn, be prepared from 2,5-dialkoxy-3-halogeno-4-hydroxytetrahydrofuranhaving formula (IX) below, in which Hal designates chlorine or bromineand R has the meaning indicated above.

In practice, to effect reactikon A, a procedure in accordance with (a)or (b) is followed:

(a) Use of the Amine in Stoichiometric Quantity

There is heated at a temperature between 50° and 100° C. for example, ina boiling water bath for several hours, preferably between 20 and 110hours, a mixture which contains a 2,5-dialkoxy-3, 4-epoxytetrahydrofuran and a stoichiometric quantity of the amine, eitherwithout solvent or in aqueous or aqueous alcoholic solution. At the endof the heating period the solvent is evaporated off if required, and thecompound of formula (III) is isolated by distillation, crystallizationor any other appropriate method. The aqueous alcohol solution cancomprise between about 10 to 90 percent of an alcohol such as methanol,ethanol orisopropanol.

(b) Use of Excess Amine

In this alternative procedure, after the end of the heating period theremaining amount of amine is driven off under reduced pressure, as wellas the solvent if necessary, and the product is isolated as indicatedabove. Generally, the molar ratio of amine to epoxy tetrahydrofuran willrange from about 50:1 to 1.5:1.

METHOD B

Reaction of an excess of the amine having formula VII wherein R₁ and R₂have the meaning indicated above, preferably, in the presence of analkali metal hydroxide, such as sodium or potassium hydroxide with acompound having formula (IX), according to the following scheme:##STR8##

The alkali metal hydroxide can be used in stoichiometric or in slightexcess with respect to compound (IX).

To effect reaction B, a procedure in accordance with (c) or (d) isfollowed.

(c) Introduction of Alkaline Metal Hydroxide After Heating

There is heated in a boiling water bath, for example, for several hours,preferably between 20 and 110 hours, a reaction mixture which contains a2,5-dialkoxy-3-halogeno-4-hydroxytetrahydrofuran [compound of formulaIX)] and an excess of the amine having formula (VII). The molar ratioamine:tetrahydrofuran ranges from 50:1 to 2:1 and preferably, there areused 5 moles or more amine per mole of compound of formula (IX). Anaqueous or an aqueous alcoholic solution as defined above can beemployed. The concentration of the amine solution is not of primaryimportance, but it is preferable to use a solution wherein the amineconcentration ranges between about 5 to 10 moles/liter.

After the end of the heating period there is added in the form of a 10 Nsolution, an alkali metal hydroxide, such as sodium or potassiumhydroxide, in equimolar quantity with reference to the compound offormula (IX) which was originally introduced. This is followed byevaporation to dryness under reduced pressure. The residue is taken upin alcohol such as ethyl alcohol and the mineral salts are eliminated byfiltration. There is a repeated evaporation to dryness under reducedpressure. The compound of formula (II) is separated from the residue bydistillation, crystallization or by any other suitable separationtechnique.

(d) Introduction of the Alkaline Metal Hydroxide Before Heating

As a variant of procedure (c), sodium hydroxide of potassium hydroxideis introduced at the start, before heating is commenced. The remainingprocedure is that described above for procedure (c).

The present invention also relates to a process for the preparation ofthe quaternary ammonium salts of formula (IV) by reaction of aquaternizing agent R₃ X on a compound having formula (III). Asquaternizing agent there can be used lower C₁ -C₄ alkyl halides,substituted or unsubstituted benzyl halides, lower dialkyl sulfates,lower alkyl tosylates and lower alkyl mesylates, said lower alkylshaving 1 to 4 carbon atoms. This reaction is effected according to thefollowing scheme: ##STR9##

There is added, for example, drop by drop, to a compound of formula(III) in ether solution, with cooling, a stoichiometric quantity of thequaternizing agent. The quaternary ammonium salt separates out. Themixture is allowed to stand, the solvent is decanted, the residue iswashed with ether, and thereafter is dried under vacuum.

The present invention further relates to the use of (1) aminatedγ-dialdehydes of formula (I), (2) the quaternary ammonium salts offormula (II) (3) the acid hydrolysis product of a2,5-dialkoxy-3-amino-4-hydroxy tetrahydrofuran or its N-substitutedderivative of formula (III), (4) the acid hydrolysis product of aquaternary ammonium salt having formula (IV), (5) the acid hydrolysisproduct of a tetraalkyl acetal having formula (V), and (6) the acidhydrolysis product of the quaternary ammonium salt of a tetraalkylacetal having formula (VI), for the coloring of the skin and thestrengthening or the restructuring of the hair.

It has been found that aminated γ-dialdehydes, of the present inventionimpart to the skin a color which is similar to that which it acquires bymore or less lengthy exposure to the sun or to ultraviolet rays. Theability of the aldehydes of the present invention to color the skinvaries according to the degree of substitution of the amino group andaccording to the nature of the substituents.

It has also been observed that the most active compounds are thesecondary amines and next the primary amines and then the tertiaryamines. Quaternary compounds do not color the skin but are usefullyemployed to strengthen or restructure the hair.

The present invention thus also relates to a cosmetic composition forcoloring the skin comprising a cosmetic carrier and at least oneaminated γ-dialdehyde whose N atom is nonsubstituted, mono-substitutedor di-substituted. The pH of this composition can range from 2 to 7,preferably between 2 and 5. The cosmetic carrier can be, for instance,an aqueous solution, an aqueous alcoholic solution containing, forinstance, about 10%-90% of a lower alkanol such as ethanol andisopropanol, an oleo alcohol creme, a gel or a fluid emulsion called"milk". Moreover, it can be packaged under pressure in an aerosolcontainer together with an aerosol propellant such asdichlorodifluoromethane, trichloromonofluoromethane, mixtures thereof orother conventional aerosol propellants. Additionally, the cosmeticcomposition can also include such conventional adjuvants as perfumes,thickening agents or dispersing agents. The active γ-dialdehydecomponent, as set forth in (1)-(6) immediately above, is generallypresent in amounts of about 0.5 to 12% percent by weight of the skincoloring or tanning composition.

The aminated γ-dialdehydes of the present invention effect astrengthening, restructuring or regeneration of the hair, with animprovement of its cosmetic quality.

This regeneration or restructuring generally is effected on bleachedhair or on hair that has undergone a treatment for permanents. It alsocan be used on hair which has undergone a reduction that constitutes thefirst stage of a "permanent wave" operation and before the second stagethereof, that is to say, the neutralizing operation.

This restructuring or strengthening of the hair is evidenced by a betterappearance and an improved feel, softness and liveliness of the hair andgeneral improvement of its cosmetic quality.

Usually this treatment to strengthen or restructure the hair is effectedby applying to the hair a cosmetic composition containing at least oneaminated γ-dialdehyde of formula (1) and/or a quaternary ammonium saltof formula (2), the pH of the solution being between 1.5 and 9,preferably between 2 and 5 and permitting said composition to remain incontact with the hair for a period of about 5-60 minutes at atemperature generally between about 15° and 50° C. The hair is thenrinsed and if desired rolled on curlers and dried.

Thus the present invention also relates to a cosmetic composition forstrengthening or restructuring the hair, said composition comprising anaqueous or aqueous alcoholic solution of about 20 to 70 weight percentof an alkanol such as ethanol or isopropanol of at least one aminatedγ-dialdehyde of formula (1) and/or a quaternary ammonium salt of formula(2), the pH of the solution being between 1, 5 and 9, preferably between2 and 5. The γ-dialdehyde or its quaternary ammonium salt is generallypresent in amounts of about 2 to 25 and preferably 3 to 18, percent byweight of said composition.

Such a composition can include other cosmetic ingredients and be in theform of a solution, a creme or a gel. It also can be stored underpressure in aerosol containers together with an aerosol propellant suchas dichlorodifluoromethane, trichloromonofluoromethane, their mixturesas well as other conventional aerosol propellants.

In order to better illustrate the invention, the following examples ofthe preparation of the compounds of this invention and their use aregiven below.

EXAMPLES OF PREPARATION Preparation of compounds of formula (III)

Example 1--Method A--procedure (a), preparation of 3,3'-ethylenediamino-bis-(2,5-dimethoxy-4-hydroxytetrahydrofuran) having formula:##STR10## There is heated in a boiling water bath for 108 hours amixture of: 29.2 g of 2,5-dimethoxy 3,4-epoxy tetrahydrofuran

6.08 g of 98.5% ethylene diamine and

3.5 ml of water

The development of the reaction is followed by gas chromatography. Afterthe conclusion of the heating period the water is driven off underreduced pressure, and reagents that have not reacted are eliminated bydistillation under 0.1 mm Hg, heating by means of an oil bath at 200° C.As distillation residue there are obtained 31.65 g of the compoundindicated above, in the form of a syrupy red liquid.

Example 2--Method A--procedure (b), preparation of 2,5-dimethoxy3-piperidino 4-hydroxytetrahydrofuran having the formula: ##STR11##

There is heated in a boiling water bath for 48 hours, a mixture of:

14.6 g of 2,5-dimethoxy 3,4-epoxy tetrahydrofuran

55 ml of piperidine

7 ml of water

After the conclusion of the heating period the water and excesspiperidine are driven off under reduced pressure and the product isdistilled. 19.3 g of the compound indicated above are obtained.

Example 3--Method B--procedure (c), preparation of 2,5-dimethoxy 3-amino4-hydroxy tetrahydrofuran having the formula: ##STR12##

There is heated in a boiling water bath for 20 hours a mixture of 27.4 gof 2,5-dimethoxy 3-chloro 4-hydroxytetrahydrofuran and 300 ml ofconcentrated NH₄ OH (22° Be). During this heating period there are addedin five operations at regular time intervals 150 ml of NH₄ OH. Afterconclusion of the heating period there are added 15 ml 10 N NaOH, withevaporation to dryness under reduced pressure. The residue is taken upin ethyl alcohol, filtered and distilled under vacuum. There areobtained 19.25 g of the compound indicated above.

Example 4--Method B--procedure (d), preparation of 2,5-dimethoxy3-ethylamino 4-hydroxytetrahydrofuran having the formula: ##STR13##

There is heated in a boiling water bath for 24 hours a mixture of:

18.25 g of 2,5-dimethoxy 3-chloro 4-hydroxytetrahydrofuran

91 ml of 5.48 N ethylamine

10 ml of 10 N NaOH

After 5 hours of heating there are added 45.5 ml of ethylamine assupplement.

After the conclusion of the heating period the solution is evaporated todryness under reduced pressure. The residue is taken up in alcohol andthe mineral salts are eliminated by filtration. Evaporation to drynessunder reduced pressure is repeated and by distillation, 15.3 g of thecompound indicated above are isolated.

Table 1 below summarizes Examples 1-18 illustrating the preparation andproperties of the compounds of formula (III) (including the 4 compoundsdescribed above).

The different columns of the said Table 1 indicate the Example No., thevalues of R₁, R₂, R₃, Method of preparation (A or B) and procedure (a,b, c or d), duration of the heating in hours, yield in %, boiling point,in °C./mm Hg., melting point, in °C.; percentages of C, H and N byelementary analysis, percentage of N by protometry and calculated valuesfor percentages of C, H and N.

Insofar as the melting and boiling points are concerned, it is to benoted that, as indicated above, the compounds of formulae (III) and (IV)present cis-trans isomerism at the level of the methoxy groups inpositions 2 and 5. The substituents in positions 3 and 4 can alsoincrease the number of possible isomers. In the course of preparation ofthese compounds, no attempt was made to separate the isomers and forthis reason the boiling points are often spread over a range oftemperatures that is somewhat broad. Further the melting points are notparticularly significant because they were determined on mixtures ofisomers whose proportion may vary from one procedure to the next.

It is to be noted that the melting points above 50° C. were determinedon a Koffler bench: melting points below 50° C. were not determined.

The compound of Example 14 was imperfectly separated from the startingamine, the mixture containing 78% of the compound of Example 14 and 22%of the starting amine. Those percentages were determined by measurementof the nitrogen.

Preparation of compounds of formula (IV)

Example 19--Preparation of [(2,5-dimethoxy 4-hydroxy) tetrahydrofuryl3-trimethyl ammonium] methosulfate having the formula: ##STR14##

To 1.6 g of 2,5-dimethoxy 3-dimethylamino 4-hydroxytetrahydrofuran in 10ml ether, there is added drop by drop with cooling, 0.88 ml of dimethylsulfate. The quaternary ammonium salt separates very rapidly. Themixture is allowed to stand for 2 hours and then the solvent isdecanted. The residue is washed twice with ether and dried under reducedpressure. 2.53 g of the above indicated quaternary ammonium salt arecollected, representing a 96% yield.

Example 20--Using an alternative procedure to a solution of 20.3 g of2,5-dimethoxy 3-dimethylamino 4-hydroxytetrahydrofuran in 30 ml acetone,there is added, drop by drop, a solution of 12.6 g dimethyl sulfate in30 ml acetone. The resulting solution is left standing at ambienttemperature for 16 hours. Then the mixture is heated to boiling for 3hours. An abundant precipitate is formed. The reaction mixture is thencooled to -20° C. and filtered thereby providing a yield of 85%, i.e.26.8 g of the above quaternary ammonium salt exhibiting a melting pointof 122° C.

The result of analysis of this compound appears in Table 2.

Example 21--preparation of [(2,5-dimethoxy 4-hydroxytetrahydrofuryl3-dimethyl benzyl ammonium] chloride having the formula: ##STR15##

A solution of 20.2 g of (2,5-dimethoxy 3-dimethylamino 4-hydroxy)tetrahydrofuran in 40 ml acetone is mixed with a solution of 12.7 gbenzyl chloride in 20 ml acetone. The resulting solution is leftstanding for 2 hours at ambient temperature, after which it is heatedunder reflux for 4 hours. The reaction mixture is then allowed to coolto room temperature and the precipitate that forms are filteredtherefrom.

20.3 g of the quaternary ammonium salt of the above formula whichrepresents a 64% yield is obtained, the salt exhibiting a melting pointof 178° C.

The result of the analysis of this compound appears in Table 2.

Example 22--preparation of [(2,5-dimethoxy 4-hydroxy) tetrahydrofuryl3-methyl diethyl ammonium] paratoluene sulfonate, of the formula:##STR16##

A solution of 13.0 g of 2,5-dimethoxy 4-hydroxy3-diethylaminotetrahydrofuran in 25 ml methylethylketone is mixed with asolution of 10.6 g of methyl paratoluene sulfonate in 25 mlmethylethylketone. The solutions are left in contact for 16 hours. Theprecipitate that forms are filtered, and there is obtained 8.5 g of thesought compound. Melting point: 142° C.

The mother liquors are heated to boiling for 5 hours, then cooled to-20° C. The precipitate that forms is filtered and recrystallized inacetone. There are thus obtained 7.2 g of the compound, meltingpoint=138° C.

Total yield is 68%.

Results of the analysis appear in Table 2.

Example 23--preparation of [(2,5-dimethoxy 4-hydroxy) tetrahydrofuryl3-methyl morpholinium] paratoluene sulfonate having the formula:##STR17##

A solution of 23.9 g of 2,5-dimethoxy 4-hydroxy 3-morpholinotetrahydrofuran in 50 ml methylethylketone is mixed with a solution of18.6 g of dimethyl paratoluene sulfonate in 30 ml methylethylketone. Theresulting solution is heated at reflux for 9 hours. The solvent is thenevaporated under reduced pressure and the residue is taken up in 350 mlwater. This aqueous solution is then clarified with activated charcoal,commercially available as "Norit", and the water is evaporated underreduced pressure. The residue is crystallized in a 1:2 mixture ofacetone and ethyl acetate. There are obtained 24.9 g of the aboveproduct exhibiting a melting point of 124°/128° C., which amountrepresents a 60% yield.

The result of the analyses appears in Table 2.

Example 24--preparation of [(2,5-dimethoxy 4-hydroxy tetrahydrofuryl3-methyl piperidinium] methane sulfonate having the formula: ##STR18##

A solution of 23.3 g of (2,5-dimethoxy 4-hydroxy 3-piperidino)tetrahydrofuran in 50 ml methylethylketone is mixed with a solution of11 g of methyl methane sulfonate in 30 ml methylethylketone. Theresulting mixture is heated to reflux for 7 hours after which it iscooled to -20° C. 27.8 g of the above compound are obtained incrystalline form, melting at 120°-122° C., and representing a yield of82%.

The result of the analysis appears in Table 2.

Table 2 below summarizes the characteristics of the quaternary ammoniumsalts of formula (IV) prepared above.

The different columns of Table 2 indicate the Example No., the values ofR₁, R₂, R₃ and X, the melting point, in °C., the percentage found forthe various constituents: C, H, N and Cl, by elementary analysis as wellas the theoretical percentages (calculated values).

Preparation of aminated dialdehydes having formulae (I) and (II)

Aldehydes of formulae (I) and (II) are prepared by acid hydrolysis ofcorresponding compounds of formulae (III) and (IV). Some examples ofhydrolysis are presented in the use examples which appear hereinafter.

Some of these aldehydes have been characterized by preparing their bisdinitrophenyl hydrazone hydrochloride.

Table 3 summarizes the characteristics of these compounds.

In this Table appear the meaning of R₁ and R₂, melting points withdecomposition, percentage contents of C, H, N by elementary analysis aswell as their theoretical percentages (calculated values) and finallythe corresponding formula.

    TABLE 1        Method          of Heating  Boiling Melting Analysis N% By Analysis     Example  Prepa- Period Yield Point Point Found Proto- Theoretical No.     R.sub.1 R.sub.2 R.sub.3 ration (Hours) % °C./mm Hg. °C. C% H     % N% metry C% H% N%       3 H H -- B(c) 20 79 90-98/0.1 66 43.46 7.59 8.26 8.2 44.2 7.98 8.59           43.70 7.61 8.34 5 H CH.sub.3 -- B(c) 20 62 87-91/0.3 58 47.09 7.88     8.07 7.84 47.4 8.46 7.91          47.00 7.85 8.12 4 H C.sub.2 H.sub.5 --     B(d) 24 80 98-100/0.5 <50 49.70 8.61 7.47 7.14 50.3 8.91 7.34     49.90 8.94 7.43 6 H C.sub.3 H.sub.7 -- B(d) 28 84  85-95/0.08 52 52.91     9.24 6.65 6.7 52.8 9.2 6.82          52.22 8.70 6.80 7 H      ##STR19##      -- B(d) 44 58 99-102/0.9 62 51.8851.44 8.828.91 6.296.42 6.67 52.8 9.2     6.82 8 H C.sub.4 H.sub.9 -- B(d) 44 79 103-106/0.1  52 52.71 9.55 6.46     6.4 54.8 9.6 6.4          53.86 9.29 6.23 9 H C.sub.6 H.sub.13 -- B(d)     33 80 118-126/0.1  <50 58.15 10.06 5.19 5.54 58.3 10.1 5.68     57.84 10.07 5.31 10 H CH.sub.2CH.sub.2OH -- A(b) 24 80 150-160/0.06     46.30 8.29 6.4 6.75 46.37 8.27 6.76          46.50 8.43 6.56 11 H      ##STR20##      -- B(d) 44 65 127-132/0.8  86 58.2158.33 9.429.35 5.695.72 5.38 58.7     9.4 5.7 12 H      ##STR21##      -- B(d) 34 29 137-140/0.08 <50 59.3859.35 6.846.84 5.275.43 5.84 60.2     7.12 5.86 13 H      ##STR22##      -- B(d) 33 67 130-146/0.07 <50 60.8860.76 7.177.55 5.034.97 5.55 61.6     7.52 5.53 14 H      ##STR23##      -- A(a) 45 24 150-180/0.05 --    5.43   4.53 1 H      ##STR24##      -- A(a) 108 90 -- 46.9846.58 7.947.82 7.88.0 7.88 47.75 7.95 7.95 15     CH.sub.3 CH.sub.3 -- B(c) 22 75 86-100/0.1  50 49.44 8.19 7.36 6.94 50.2     8.9   7          49.74 8.30 7.47 16 C.sub.2 H.sub.5 C.sub.2 H.sub.5     --B(d) 44 76 85-98/0.06 -- 54.77 9.52 5.77 6.03 54.7 9.7  6.4     54.62 9.47 6.03 17 CH.sub.2CH.sub.2OH CH.sub.2CH.sub.2OH -- A(b) 24 85     180-195/0.07  47.27 8.26 5.84 5.6  47.8 8.42 5.57          47.29 8.39     6.03 2 piperidinyl --  48 83 110-119/0.07  57.12 9.34 6.03 6.05 37.12     9.15 6.06 18 morpholinyl -- A(b) 72 76 108-122/0.03  51.38 8.22 5.84     5.82 51.5 8.1 6.00         51.27 8.12 5.92

                                      TABLE 2                                     __________________________________________________________________________                                      Melting                                     Example                           Point                                                                              Analysis Found                                                                            Analysis Theoretical       No.  R.sub.1                                                                          R.sub.2                                                                           R.sub.3  X.sup.-      (°C.)                                                                       C% H% N% Cl%                                                                              C% H% N% Cl%               __________________________________________________________________________    0    CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3 CH.sub.3 SO.sub.4.sup.-                                                                    122  37.93                                                                            7.09                                                                             4.17                                                                             -- 37.8                                                                             7.26                                                                             4.41                                                        38.11                                                                            7.23                                                                             4.28                             1    CH.sub.3                                                                         CH.sub.3                                                                           ##STR25##                                                                             Cl.sup.-     178  56.56 56.81                                                                      7.30 7.55                                                                        4.17 4.45                                                                        10.95                                                                            56.5                                                                             7.55                                                                             4.41                                                                             11.2              2    C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                   CH.sub.3                                                                                ##STR26##   142  53.22 53.38                                                                      7.63 7.79                                                                        3.36 3.39                                                                        -- 53.31                                                                            7.70                                                                             3.45                                                                             --                3    morpholinyl                                                                          CH.sub.3                                                                                ##STR27##   124 128                                                                            51.53 51.56                                                                      7.00 7.06                                                                        3.23  51.53                                                                            6.96                                                                             3.34                 4    piperidinyl                                                                          CH.sub.3 CH.sub.3 SO.sub.3.sup.-                                                                    120  46.01                                                                            8.05                                                                             4.16  45.59                                                                            8.24                                                                             4.09                                                   122  46.13                                                                            7.93                                __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________    Hydrochloride of Bix Dinitrophenylhydrazone of a few Aldehydes                 ##STR28##                                                                              Melting                                                                       Point                                                                         with de-                                                                      composi-                                                                           Analysis Found                                                                         Analysis-Theoretical                                  R.sub.1                                                                         R.sub.2 tion, °C.                                                                   C% H% N% C% H% N% for the formula                              __________________________________________________________________________    H H       180-188                                                                            34.78                                                                            3.02                                                                             22.46                                                                            34.95                                                                            3.66                                                                             22.92                                                                            C.sub.16 H.sub.15 O.sub.9 N.sub.9 . HCl                                       . 2H.sub.2                                   H CH.sub.3                                                                              160-165                                                                            37.44                                                                            3.51                                                                             22.19                                                                            37.40                                                                            3.69                                                                             23.09                                                                            C.sub.17 H.sub.17 O.sub.9 N.sub.9 . HCl                                       . H.sub.2 O                                  H C.sub.2 H.sub.5                                                                       160-168                                                                            39.31                                                                            3.58                                                                             22.48                                                                            38.61                                                                            3.96                                                                             22.51                                                                            C.sub.18 H.sub. 19 O.sub.9 N.sub.9 . HCl                                      . H.sub.2 O                                  H C.sub.3 H.sub.7                                                                       156-162                                                                            39.75                                                                            4.18                                                                             21.87                                                                            39.76                                                                            4.21                                                                             21.96                                                                            C.sub.19 H.sub.21 O.sub.9 N.sub.9 . HCl                                       . H.sub.2 O                                     ##STR29##                                                                            160-175                                                                            40.29                                                                            4.11                                                                             21.63                                                                            39.76                                                                            4.21                                                                             21.96                                                                            C.sub.19 H.sub.21 O.sub.9 N.sub.9 . HCl                                       . H.sub.2 O                                  H C.sub.4 H.sub.9                                                                       150-162                                                                            39.77                                                                            4.24                                                                             21.94                                                                            40.85                                                                            4.45                                                                             21.44                                                                            C.sub.20 H.sub.23 O.sub.9 N.sub.9 . HCl                                       . H.sub.2 O                                  H C.sub.6 H.sub.13                                                                      137-142                                                                            42.84                                                                            4.61                                                                             20.47                                                                            42.89                                                                            4.90                                                                             20.46                                                                            C.sub.22 H.sub.27 O.sub.9 N.sub.9 . HCl                                       . H.sub.2 O                                  H                                                                                ##STR30##                                                                            164-172                                                                            42.81                                                                            4.30                                                                             20.48                                                                            43.03                                                                            4.59                                                                             20.53                                                                            C.sub.22 H.sub.25 O.sub.9 N.sub.9 . HCl                                       . H.sub.2 O                                  H                                                                                ##STR31##                                                                            155-165                                                                            44.10                                                                            3.56                                                                             20.42                                                                            44.41                                                                            3.88                                                                             20.27                                                                            C.sub.23 H.sub.21 O.sub.9 N.sub.9 . HCl                                       . H.sub.2 O                                  __________________________________________________________________________

EXAMPLES OF USE EXAMPLE 34

The following tanning composition is prepared:

    ______________________________________                                        8% solution of 2-amino 3-hydroxy succinic aldehyde                                                        40 ml                                             ethyl alcohol, 96° titer                                                                           40 ml                                             white glycerol               2 ml                                             perfume                     1 g                                               Na.sub.2 CO.sub.3, q.s.p. for pH = 2                                          water, q.s.p.               100 ml                                            ______________________________________                                    

This composition is applied regularly to all parts of the body that onewishes to tan.

At the end of 2 or 3 minutes a light coloration appears which after 15minutes assumes a very natural brown tone. This shade is ratherresistant. However, if the shade is considered to be too dark, it can belightened by washing with water and soap, makeup remover milk or eau deCologne.

A product of this kind is much appreciated especially for "harmonizing"or "touching up" e.g. when there are white marks left by eyeglass frameson the nose or by shoulder straps on the shoulders.

EXAMPLE 35

The following composition in the form of white milk is prepared:

    ______________________________________                                        cetyl stearyl alcohol, partly oxyethylenated (sold                            commercially as "Sipol wax" by the Sinnova company                            (France)                     2.5 g                                            wheat starch                 2 g                                              a mixture of methyl, ethyl, butyl and benzyl esters of                        para hydroxybenzoic acid (sold commercially as "Nipa                          ester 82521" by Nipa company (US)                                                                          0.19 g                                           phenyl polysiloxane (sold commercially as "Rhodorsil oil                      47 V.300" by Rhone-Poulenc company (France)                                                                0.2 g                                            10% solution of 2-methylamino 3-hydroxysuccinic                               aldehyde                     20 g                                             Na.sub.2 CO.sub.3, 2N, q.s.p. for pH 3                                        perfume                      0.5 g                                            water, q.s.p.                100 g                                            ______________________________________                                    

When evenly applied to the skin, this milk affords a golden colorationin less than 10 minutes. The color reaches its maximum in at least anhour, looking just like natural tan. The coloration is resistant tobaths, even in sea water.

EXAMPLE 36

The following oleo-alcohol composition is prepared:

    ______________________________________                                        colza oil                   2 g                                               isopropyl myristate         25 g                                              ethyl alcohol, 96° titer                                                                           60 g                                              perfume                     0.5 g                                             18% solution of 2-benzylamino 3-hydroxysuccinic                               aldehyde (the pH being adjusted to 3 by means of                              Na.sub.2 CO.sub.3           12.5 g                                            ______________________________________                                    

This composition is introduced into aerosol cans and, after sealing, 70g of dichlorodifluoromethane are added. This composition is sprayed onany part of the body that is to be tanned. At the end of 15 minutes alight coloration begins to appear, which then darkens to a bronzed hue.This color resists fresh water, sea water, washing with soap, and makeupremovers.

EXAMPLE 37

There is prepared a solution of 2-amino 3-hydroxy succinic aldehyde, byheating for 10 minutes in a boiling water bath, 519 mg of 2,5-dimethoxy3-amino 4-hydroxy tetrahydrofuran in 10 cc N HCl. The pH of thissolution is adjusted to between 3 and 4 by the addition thereto ofsodium carbonate.

Bleached hair is impregnated with the above solution and heated under ahood for 30 to 45 minutes. At the end of this contact period, the hairis shampooed, rinsed and dried. The thus treated hair has an improvedappearance, is flexible and more lively.

EXAMPLE 38

A solution of 3-hydroxy 2-propylaminosuccinic aldehyde is prepared byheating for one hour in a boiling water bath 2.78 g of 2,5-dimethoxy4-hydroxy 3-propylamino tetrahydrofuran in 33.5 cc 1 N HCl. The pH ofthis solution is adjusted to between 3 and 4 by the addition thereto ofsodium carbonate.

As indicated in Example 37, previously bleached hair is treated with thesolution thus prepared. The results are just as good as those reportedin Example 37.

EXAMPLE 39

A solution of 2,2'-ethylene diamino bis (3-hydroxysuccinic) aldehyde isprepared by heating for one hour over a boiling water bath, 608 mg of3,3' ethylene diamino bis(4-hydroxy 2,5-dimethoxy) tetrahydrofuran in 10ml 1 N HCl. The pH of this solution is adjusted to 3.5 by the additionthereto of sodium carbonate.

As indicated in Example 37, previously bleached hair is treated with thesolution thus prepared. The results are just as good as those achievedin Examples 37 and 38.

EXAMPLE 40

A solution of 3-hydroxy 2-piperidino succinic aldehyde is prepared byheating for 5 hours over a boiling water bath 3.5 g. of 2,5-dimethoxy3-hydroxy 4-piperidino tetrahydrofuran in 40 cc of 1 N HCl. The pH ofthis solution is adjusted to 4 by the addition thereto of sodiumcarbonate.

As indicated in Example 37, previously bleached hair is treated with thesolution thus prepared and the results obtained are just as good asthose reported in Examples 37-39.

EXAMPLE 41

A solution of quaternary ammonium salt of 3-hydroxy 2-trimethylammoniumsuccinic aldehyde is prepared by dissolving 2.53 g. of 2,5-dimethoxy4-hydroxy 3-trimethylammonium tetrahydrofuran methosulfate in 15 ml 1 NNaOH and adding to this solution after it has stood overnight, atambient temperature, 15 ml of 2 N HCl and heating for 43 hours over aboiling water bath. The pH of this solution is adjusted between 3 and 4by the addition thereto of sodium carbonate.

As indicated in Example 37, previously bleached hair is treated with thesolution thus prepared. The results obtained are just as good as in theprevious examples.

EXAMPLE 42

The following composition is prepared:

    ______________________________________                                        M solution of 2-isopropylamino 3-hydroxy                                      succinic aldehyde          50 cc                                              ethyl alcohol, 96° titer                                                                          40 cc                                              glycerine                  2 cc                                               perfume                    0.1 cc                                             sodium bicarbonate, q.s.p. pH 3                                               water, q.s.p.              100 cc                                             ______________________________________                                    

The resulting clear brown liquid when applied to those parts of the bodydesired to be tanned, imparts thereto in about one-half hour, an ambershade that can be essentially removed by washing with soapy water.

EXAMPLE 43

The following composition is prepared:

    ______________________________________                                        0.372 M solution of 2-butylamino 3-hydroxy                                    succinic aldehyde         15 cc                                               oleyl alcohol condensed with 10 moles                                         ethylene oxide            5 g                                                 carboxymethyl cellulose   2 g                                                 orthohydroxy quinoline sulfate                                                                          0.1 g                                               silicone oil              1 g                                                 2N sodium carbonate, q.s.p.                                                                             pH 3                                                perfume                   1 g                                                 water, q.s.p.             100 g                                               ______________________________________                                    

This composition is applied to the skin to be tanned. The desired, verynatural brown color appears ten minutes following application. Theresistance of the coloration achieved to even soapy water increases withthe length of the application time.

EXAMPLE 44 Tanning Milk

    ______________________________________                                        cetyl stearyl alcohol condensed with 13 moles                                 ethylene oxide             7 g                                                phenyl polysiloxane (sold under the name                                      "Rhodorsil Oil 47 V300" by Rhone-Poulenc                                      company)                   1 g                                                diethyleneglycol stearate  6 g                                                methyl parahydroxy benzoate                                                                              0.1 g                                              propyl parahydroxy benzoate                                                                              0.1 g                                              0.411 M solution of 2-hexylamino                                              3-hydroxy succinic aldehyde                                                                              25 cc                                              2N sodium carbonate, q.s.p.                                                                              pH 2.5                                             water, q.s.p.              100 g                                              ______________________________________                                    

When applied to the skin, this bronzing or tanning milk reaches maximumintensity of coloration in about two hours. The coloration is a verynatural golden shade which resists removal by water.

EXAMPLE 45 Tanning Cream

    ______________________________________                                        cetyl stearyl alcohol condensed with 13 moles                                 of ethylene oxide          2.6 g                                              cetyl alcohol              2.6 g                                              stearic acid               0.6 g                                              castor oil                 6.85 g                                             sweet almond oil           1.3 g                                              C.sub.12 -C.sub.14 alcohol condensed with 10.5 moles                          ethylene oxide             0.3 g                                              ethyl para amino benzoate  0.2 g                                              isopropyl myristate        4.5 g                                              perfume                    0.3 g                                              0.372 M solution of 2-cyclohexyl amino 3-                                     hydroxy succinic aldehyde  35 cc                                              2N sodium carbonate, q.s.p pH 3.5                                             water, q.s.p.              100 cc                                             ______________________________________                                    

The resulting cream is colored light beige and when applied on theportions of the skin to be tanned, the coloration starts to appear inabout 15 minutes and reaches its maximum intensity in about 2 hours. Thecolor obtained is a pretty natural chestnut shade which resists quitewell even soapy water.

EXAMPLE 46

10 grams of previously bleached hair are impregnated with 25 cc of asolution of 0.425 M 2-hydroxy 3-trimethylammonio succinic aldehydeprepared by acid hydrolysis of the corresponding tetrahydrofuran. The pHof the solution is adjusted to 3 by the addition thereto of sodiumbicarbonate. The solution is permitted to remain in contact with thehair for 30 minutes at a temperature of 50° C., after which the hair isrinsed and dried. As a result of this treatment the hair has an improvedappearance, is more flexible and more soft.

EXAMPLE 47

To hair which has previously been permanently waved there is applied a0.512 M solution of 2-hydroxy 3-dimethyl benzyl ammonio succinicaldehyde prepared by acid hydrolysis of the correspondingtetrahydrofuran. The pH of said solution being is adjusted to 4 by theaddition thereto of sodium bicarbonate. This solution is permitted toremain in contact with the hair for 40 minutes at 30° C., after whichthe hair is rinsed and dried. The thus treated hair has a very agreeablelook and is more soft to the touch than the hair prior to saidtreatment.

EXAMPLE 48

Bleached hair is impregnated for a period of 30 minutes at 30° C. with a0.362 M solution of 2-hydroxy 3-diethylmethyl ammonia succinic aldehydeprepared by acid hydrolysis of the corresponding tetrahydrofuran. The pHof the solution is adjusted to 3.5 by the addition thereto of sodiumbicarbonate. The thus treated hair is then rinsed after which a hairsetting lotion comprising 40% aqueous solution of a copolymer ofpolyvinyl pyrrolidone and vinyl acetate having a viscosity of 3.5 to 4centipoises in 5% solution in ethanol having a pH of 3.5 is appliedthereto. The hair is then rolled on curlers and dried. Excellent resultsare obtained including the imparting of a brilliant sheen to the hair.

EXAMPLE 49

Previously bleached hair is impregnated with a 0.437 M solution of2-hydroxy 3-(methyl morpholino) succinic anhydride, the pH of which hadbeen adjusted to 2.5 by the addition thereto of powdered sodiumcarbonate. The solution remained in contact with the hair for a periodof 30 minutes at a temperature of 45° C. The hair was then rinsed andset in the customary way.

After drying the hair is more easy to style and less electric than hairnot treated with said solution.

EXAMPLE 50

To previously bleached hair there is applied for a period of about 30minutes at 50° C. the following solution:

    ______________________________________                                        0.484 M solution of 2-hydroxy 3-(methyl piperidino)                           succinic aldehyde           100 cc                                            sodium bicarbonate, q.s.p.  pH 3                                              ______________________________________                                    

Thereafter the hair is rinsed, rolled on curlers and dried under a hood.The hair thus treated is lively and less electric and more easy to stylethan hair not treated as described.

EXAMPLE 51

To hair that has been previously bleached and then dyed, there isapplied a 0.353 M solution of 2-diethylamino 3-hydroxy succinicaldehyde, the pH of which has been adjusted to 2.5 by the additionthereto of sodium carbonate. The solution is permitted to remain incontact with the hair for a period of 30 minutes at 50° C. The hair isthen rinsed, set in the usual fashion and dried under a hood. The thustreated hair is more brilliant and less subject to tangling than hairnot treated with the solution described above.

EXAMPLE 52

Previously bleached hair is shampooed with an acidic cationic shampoocomposition and then dried. Thereafter the hair is impregnated with 100cc of a 0.268 M solution of 2-bis (β-hydroxyethyl amino 3-hydroxysuccinic aldehyde, the pH of which has been adjusted to 2.5 by theaddition thereto of sodium bicarbonate, for a period of about 30 minutesat 45° C. To the thus treated hair there is then applied the followinghair setting solution:

    ______________________________________                                        copolymer of polyvinylpyrrolidone and vinyl acetate                           having a viscosity of 3.5 to 4 centipoises in 5%                              solution in ethanol         5 g                                               ethyl alcohol, 96° titer                                                                           25 cc                                             trimethyl cetyl ammonium bromide                                                                          0.1 g                                             powdered sodium bicarbonate, q.s.p.                                                                       pH 2.5                                            water, q.s.p.               100 cc                                            ______________________________________                                    

The hair is then rolled on curlers and again saturated with the abovehair setting solution. After drying, the hair is lively and holds a goodset.

What is claimed is:
 1. Aminated γ-dialdehyde having the formula##STR32## wherein R₁ and R₂ each independently are selected from thegroup consisting of hydrogen, alkyl having 1-6 carbon atoms,hydroxy-alkyl wherein the alkyl moiety has 1-6 carbon atoms, cycloalkylhaving 3-6 carbon atoms, aryl, alkaryl wherein the alkyl moiety has 1-6carbon atoms, (2,5-dialkoxy 4-hydroxy)-3-tetrahydrofuryl wherein each ofthe alkoxy moieties has 1-4 carbon atoms, β-N-[(2,5-dialkoxy4-hydroxy)-3-tetrahydrofuryl]-aminoethyl wherein each of the alkoxymoieties has 1-4 carbon atoms, and together with the nitrogen atoms towhich they are attached form a heterocycle selected from the groupconsisting of piperidinyl and morpholinyl.
 2. Quaternary ammonium saltof aminated γ-dialdehyde having the formula ##STR33## wherein R₁ and R₂each independently are selected from the group consisting of alkylhaving 1-6 carbon atoms, hydroxyalkyl wherein the alkyl moiety has 1-6carbon atoms, cycloalkyl having 3-6 carbon atoms, aryl, alkaryl whereinthe alkyl moiety has 1-6 carbon atoms, (2,5-dialkoxy4-hydroxy)-3-tetrahydrofuryl wherein each of the alkoxy moieties has 1-4carbon atoms, β-N-[(2,5-dialkoxy4-hydroxy)-3-tetrahydrofuryl]-aminoethyl wherein each of the alkoxymoieties has 1-4 carbon atoms, and together with the nitrogen atom towhich they are attached form a heterocycle selected from the groupconsisting of piperidinyl and morpholinyl, R₃ is selected from the groupconsisting of lower alkyl having 1-4 carbon atoms and benzyl,substituted or not, and X⁻ represents a member selected from the groupconsisting of chloride, bromide, iodide, methosulfate, ethosulfate,paratoluene sulfonate and methane sulfonate.
 3. Aminated γ-dialdehydehaving the formula ##STR34## wherein R₁ and R₂ together with thenitrogen atom to which they are attached form a heterocycle selectedfrom the group consisting of piperidinyl and morpholinyl, and thequaternary ammonium salts thereof.
 4. An acid solution of the aminatedγ-dialdehyde of claim 3, said acid being present in a concentrationeffective to stabilize said aminated γ-dialdehyde.
 5. Aminatedγ-dialdehyde of claim 3, wherein said heterocycle is piperidinyl. 6.Aminated γ-dialdehyde of claim 3, wherein said heterocycle ismorpholinyl.